Oxime ethers and pesticidal preparations containing them

ABSTRACT

New oxime ethers and pesticidal and herbicidal preparations containing them are disclosed. The oxime ethers correspond to the formula ##SPC1## 
     Wherein R 1  is a hydrogen atom or a lower alkyl radical; R 2  is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical; or wherein R 1  and R 2  form part of a saturated or unsaturated carbocycle or a 5-, 6- or 7-membered heterocycle; R 3  is nitro, trifluoromethyl, formyl, lower carbalkoxy, sulfamyl or mono- or di-lower alkyl fulfamyl radical; R 4-  and R 5  each is a hydrogen or halogen atom, an amino, mono- or di-lower alkyl amino, lower alkoxy, cycloalkoxy, lower alkylthio, nitro, lower carbalkoxy, arylthio, lower aralkylthio or lower alkyl group, or 5-, 6- or 7-membered heterocycle.

BACKGROUND OF THE INVENTION

The present invention provides new oxime ethers and pesticidal preparations containing them. The oxime ethers correspond to the formula ##SPC2##

wherein R₁ is a hydrogen atom or a lower alkyl radical; R₂ is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical; or wherein R₁ and R₂ form part of a saturated or unsaturated carbocycle or a 5-,6-or 7-membered heterocycle; R₃ is a nitro, trifluoromethyl, formyl, lower carbalkoxy, sulfamyl or mono- or di- lower alkylsulfamyl radical; R₄ and R₅ each is a hydrogen or halogen atom, an amino, mono- or dilower alkylamino, lower alkoxy, cycloalkoxy, lower alkylthio, nitro, lower carbalkoxy, arylthio, lower aralkylthio group or 5-, 6- or 7-membered heterocycle.

R₁ in the above formula stands for a lower alkyl radical. Such radicals contain 1 to 4 carbon atoms and may be branched or unbranched such as the methyl and ethyl groups or the normal or iso-propyl or butyl group or secondary or tertiary butyl group. Preferred groups, however, are besides the hydrogen atom the methyl and ethyl radicals.

R₂ stands for an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical. The aliphatic radical may be branched or unbranched, saturated or unsaturated. Preferably such radicals contain up to 8 carbon atoms and are alkyl or alkenyl radicals which may be substituted or unsubstituted. Suitable substituents are for instance halogen atoms, such as fluorine, chlorine or bromine or hydroxy or alkoxy groups. The cycloaliphatic radicals contain 3 to 8 carbon atoms and may be saturated or unsaturated and mono- or polycyclic. As a rule they contain 3 to 12 carbon atoms and are saturated. They preferably are mono- or bicyclic and have 3 to 7 ring members. The araliphatic radicals contain in the aromatic moiety at least one benzene nucleus and in the aliphatic moiety preferably an unbranches chain containing 1 to 4 carbon atoms. This aliphatic chain may be saturated or unsaturated, substituted or unsubstituted. Suitable substituents are hydroxy groups and halogen atoms, such as chlorine and especially bromine. Suitable chains contain 2 carbon atoms and are saturated; they may also contain one or two bromine atoms or one double bond. Aromatic radicals are to be understood as being substituted or unsubstituted phenyl radicals or condensed ring systems. The preferred embodiment are substituted and unsubstituted phenyl radicals. Suitable substituents on the phenyl moiety are e.g. halogen atoms such as fluorine and especially chlorine, bromine and iodine; lower alkyl and alkoxy groups containing 1 to 4 carbon atoms; hydroxy groups; amino groups which may be substituted by one or two lower alkyl, lower alkoxyalkyl or lower alkanol radicals; nitro groups; lower alkyl carbamoyl radicals; phenoxy groups which may be substituted by one or more of the substituents enumerated above for the phenyl radical especially by nitro groups. The heterocyclic radicals coming into consideration particularly are 5- or 6-membered and contain at least one oxygen or sulfur especially however nitrogen atom. These heterocycles may be substituted, preferably by lower alkyl radicals, especially the methyl group. Examples of such heterocycles are i.a. pyridine and quinaldine compounds.

R₃ stands for a trifluoromethyl, formyl, nitro, lower carbalkoxy, sulfamyl or mono- or di-lower alkysulfamyl group. The alkyl moieties of the carbalkoxy and alkylsulfamyl group contain 1 to 4 carbon atoms and may be branched or unbranched. Preferred alky moieties contain 1 or 2 carbon atoms. However, suitable substitutent are not limited to the above enumeration. Thus also halogenalkyl groups quite generally may be used. Moreover, halogen atoms such as chlorine, bromine and iodine; alkyl groups containing 1 to 6 carbon atoms, the carboxyl group; lower alkyl- or aryl-, especially phenylcarbamyl groups; the sulfonic acid groups; and lower alkylsulfonyl groups may be used likewise.

R₄ and R₅ each stands for a hydrogen or halogen atom, a lower alkyl, amino, mono- or di- lower alkylamino, lower alkoxy, cycloalkoxy, lower alkylthio, lower carbalkoxy, arylthio, lower aralkylthio, nitro or heterocyclic radical. The halogen atoms may be elected from fluorine, bromine, iodine and especially chlorine. The lower alkyl moieties enumerated above contain 1 to 4 carbon atoms and may be branched or unbranched. The heterocyclic radicals are 5-, 6- or 7-membered, especially 5- or 6-membered, and contain as hetero- atoms one or more oxygen, sulfur or especially nitrogen atoms. Such heterocyclic radicals are i.a. the pyridino and morpholino radical. The cycloalkoxy radicals are 3 to 8-membered, especially however 6-membered. Representative of such radicals is the cyclohexoxy radical. Especially suitable oxime ethers are those which correspond to the formulae ##SPC3##

wherein R₁, R₂, R₃, R₄ and R₅ have the meanings given above. More particularly R₃ stands for a nitro, trifluoromethyl, formyl, methylcarbonyl, methylsulfamyl or a dimethylsulfamyl radical. R₄ for a hydrogen or chlorine atom, an amino, methyl amino, dimethyl amino, isopropylamino, methoxy, ethoxy, benzylmercapto or morpholino group, and R₅ for a hydrogen atom, a methyl, sec.butyl, carbomethoxy, nitro or cyclohexoxy radical.

From among the compounds of formula (III) those should be specially mentioned which correspond to the formulae ##SPC4##

wherein R₁ and R₂ have the meanings given above and R and R' each is hydrogen, lower alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.butyl, tert.butyl amyl or cycloalkyl, such as cyclopentyl or cyclohexyl.

From among the compounds of formulae (II) and (III) those are preferred which correspond to the formula ##SPC5##

wherein R₁ and R₂ have the above meanings. More particularly R₁ may stand for hydrogen and R₂ for a substituted phenyl radical. Such compounds correspond to the formulae ##SPC6##

and more specifically to the formulae ##SPC7##

wherein R₃, R₄ and R₅ have the meanings given above and X and X' each stands for halogen. More specifically X represents chlorine bromine and iodine, whereas X' stands for chlorine.

The oxime ethers of the formulae (I) to (VI) may be derived from aliphatic, araliphatic, aromatic or heterocyclic aldehydes or ketones, and also from quinones and endocyclic ketones for example fluorenone, indanone, acenaphthenone, anthrone, N-methylpyridone, N-methylpiperidone, furfurol or nitrofurfurol.

Preferred use is made of oxime ethers derived from aliphatic aldehydes or ketones, from araliphatic aldehydes or ketones, or from aromatic or heterocyclic aldehydes or ketones.

Suitable aliphatic aldehydes are simply constituted aldehydes for example acetaldehyde, propionaldehyde, butyraldehyde or aldehydes having a longer chain, for example heptaldehyde, stearaldehyde or unsaturated aldehydes for example crotonaldehyde. Suitable aliphatic ketones are simple ketones for example acetone, methylethyl ketone, hexanone-(3), diisopropylketone, mesityl oxide, and phorone. Suitable araliphatic or aromatic aldehydes and ketones are cinnamic aldehyde, hydrocinnamic aldehyde, halogen adducts or cinnamic aldehyde for example dibromo-cinnamic aldehyde, diiodo-cinnamic aldehyde, acetophenone, propiophenone, benzaldehyde, nuclear halogenated, alkylated, nitrated and alkoxylated benzaldeyhdes. Examples of suitable cyclic ketones are cyclopentanone, cyclohexanone, cycloheptanone as well as their cyano derivatives. Suitable heterocyclic ketones and aldehydes are, for example, picoline aldehyde nicotine aldehyde, isonicotine aldehyde and N-alkylpiperidones.

If such aldehydes or ketones contain aromatic radicals, their suitably substituted derivatives may likewise be used. These substituents may be of a non-functional kind, for example halogen atoms, nitro or nitroso groups, or of a functional kind or derived from functional substituents, being, for example hydroxyl, acyloxy, carbamoyloxy, alkoxy, aryloxy, thiol, acylthio, alkylthio, trifluoromethyl, cyano, formyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, carboxy or carbalkoxy groups.

By virture of their broad biocidal spectrum the new oxime ethers offer the special advantage that they are suitable for combating a very wide variety of vegetable and animal pests. They are suitable not only for use as herbicides, which is the preferred utility, but when used in a concentration that does not produce any phytotoxic effects, they are very useful in plant protection for combating harmful micro-organisms, such as phytopathogenic fungi, for example Alternaria solani, Phytophthora infestans and Septoria apii, and act also against harmful insects, acarides, nematodes and their ova and larvae. They may also be used quite generally as microbicides, for example against Aspergillus species, and as insecticides, for example against midges and flies.

The oxime ethers according to this invention may be used per se or in admixture with suitable carriers. Such carriers may be solid or liquid. The pesticidal preparations thus formed may therefore contain a solid carrier, a solvent diluent, dispersant, wetting agent, adhesive, fertilizer and/or other known pesticides.

For the manufacture of solutions of compounds of the general formula (I) for direct spraying there may be used, for example, petroleum fractions of a high to medium boiling range, for example Diesel oil or kerosene, coal tar oil and oils of a vegetable or animal origin, as well as hydrocarbons for example alkylated naphthalenes, tetrahydronaphthalene if desired in conjunction or admixture with xylene mixtures, cyclohexanels, ketones, chlorinated hydrocarbons for example trichloroethane or tetrachloroethane, trichlorethylene, tri- or tetrachlorobenzene. It is advantageous to use organic solvents boiling above 100°C.

Aqueous forms of applications are prepared most advantageously from emulsion concentrates, pastes or wettable spray powders by addition of water. Suitable emulsifying or dispersing agents are non-ionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids containing a long-chain hydrocarbon residue of about 10 to 20 carbon atoms with ethylene oxide, for example the condensation product of octadecyl alcohol with 25 to 30 mols of ethylene oxide, or of sybean fatty acid with 30 mols of ethylene oxide, or of commercial oleylamine with 15 mols of ethylene oxide, or of dodecylmercaptan with 12 mols of ethylene oxide. From among suitable anionic emulsifiers, there may be mentioned the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic or abietic acid or of mixtures of these acids, or the sodium salt of a petroleumsulphonic acid. Suitable cationic dispersants are quaternary ammonium compounds, for example cetyl pyridinium bromide or dihydroxyethyl benzyl dodecyl ammonium chloride.

For the manufacture of dusting and casting preparations, there may be used as solid vehicles talcum, kaolin, bentonite, calcium carbonate, calcium phosphate, or coal, cork meal, wood meal or other materials of vegetable origin. It is also very advantageous to manufacture preparations in granular form. The various forms of application may contain the usual additives for improving the distribution, the adhesion, the stability towards rain or the penetration; as such substances there may be mentioned fatty acids, resin, glue, casein and alginates.

The preparations of this invention may be used by themselves or in conjunction or admixture with conventional pesticides, especially insecticides, acaricides, nematocides, bactericides or further fungicides or herbicides.

Especially potent herbicides are those preparations which contain as active ingredient a compound of the formula ##SPC8##

wherein R₁ represents a hydrogen atom or analiphatic radical and R₂ an aliphatic radical or an unsubstituted or substituted phenyl group, A represents --NO₂, --CHO, --COOH or COO alkyl, and B stands for hydrogen, --NO₂, --COOH, --COOalkyl or chlorine. The phenyl radical R₂ may carry various substituents, for example halogen atoms, nitro, alkyl, hydroxyl or alkoxy groups and/or carbamoyloxy groups.

Particularly potent herbicides are the compounds of the formula (Ia) wherein R₁ and R₂ have the following meanings: ##SPC9##

Especially useful acaricides are those preparations which contain as active ingredient a compound of the formula ##SPC10##

wherein R₁ represents a hydrogen atom and R₂ a phenyl radical which may be substituted by halogen atoms or alkyl or alkoxy groups, or wherein R₁ and R₂ represent alkyl radicals or are part of an isocyclic residue.

Especially potent are the compounds of the formula ##SPC11##

The active ingredients of formula I may be manufactured according to known methods, such as e.g.:

A salt of a ketoxime or aldoxime of the formula ##EQU1## wherein R₁ and R₂ have the above meanings and Mc stands for a metal atom, preferably an alkali metal atom- is reacted with a halogeno-benzene of the formula ##SPC12##

wherein R₃ to R₅ have the above meanings and Hal represents a fluorine, chlorine, bromine or iodine atom.

The reaction may be carried out in a solvent, for example in ethanol, methanol, acctonitrile or dioxan, as a rule at room temperature; in many cases it is accompanied by a spontaneous rise in temperature. The oxime ethers obtained in this mannor are very easy to isolate by diluting the reaction solution with water. The ethers precipitate and may, if desired, be recrystallized. This process may be varied in that following upon the formation of the oxime ether one or several groups, R₃, R₄, R₅, R₆ are subsequently converted.

More especially, halogen atoms R₅ and/or R₆ may be exchanged for compounds containing active hydrogen atoms, thus for example for ammonia, primary or secondary aliphatic, araliphatic or aromatic amines, alcohols, phenols, alkanethiols or thiophenols.

The oxime ethers accessible in this manner may take the syn-form or the anti-form. As a rule, they are obtained in the form of a mixture of isomers, which can be resolved into the two forms by a usual operation, for example crystallization or adsorption. For the manufacture of the preparations of this invention, it suffices to use the mixture of isomers as obtained by the reaction.

The present invention further includes new oxime ethers of the general formula ##SPC13##

wherein R₁ and R₂ have the above meanings and R₄ represents a trifluoromethyl, formyl, unsubstituted or substituted carboxyl or possibly alkylated sulphamyl residue, and R₅ represents a hydrogen atom or a nitro group, or wherein R₄ stands for the nitro group and R₅ for a possible esterified carboxyl group.

The following Examples illustrate the invention:

EXAMPLE 1 ##SPC14##

A solution of sodium ethylate prepared from 11.5 parts of sodium and 500 parts by volume of absolute ethanol is added to 76 parts of anisaldehyde in 400 parts by volume of absolute ethanol. During 10 minutes at 40°C 101 parts of 4-chloro-1,3 -dinitrobenzene in 300 parts by volume of absolute ehtanol are added drop, the temperature rising to 65°C. The batch is cooled to room temperature, diluted with water, filtered and recrystallized from dimethylformamide-ethanol. The product melts at 187°- 17.5°C.

EXAMPLE 2 ##SPC15##

A solution of sodium ethylate prepared from 13.1 parts of sodium and 300 parts by volume of absolute ethanol is added drop by drop during 30 minutes, at room temperature, to a solution of 82 parts of ortho-methoxybenzaldehydeoxime and 115 parts of 4-chloro-1,3-dinitrobenzene in 1000 parts by volume of acetonitrile. After 4 hours, the batch is diluted with 3000 parts by volume of water, filtered and recrystallized from toluene-acetone. The product melts at 184° - 184.5°C.

EXAMPLE 3 ##SPC16##

A solution of sodium ethylate prepared from 18.5 parts of sodium and 500 parts by volume of absolute ethanol is added drop by drop during 30 minutes at room temperature to a solution of 90 parts of cyclohexanone oxime and 162 parts of 4-chloro-1,3-dinitrobenzene in 500 parts by volume of acetonitrile. After 4 hours, the batch is diluted with water filtered and recyrstallized from acetonitrile. The product melts at 105.5°-106°C.

EXAMPLE 4 ##SPC17##

A solution of sodium ethylate prepared from 12 parts of sodium and 250 parts by volume of absolute ethanol is added drop by drop at room temperature to a solution of 50.5 parts of methyl-isopropoyl ketonoxime and 101.3 parts of 4-chloro-1,3-dinitrobenzene in 400 parts by volume of acetonitrile, while stirring. After 12 hours, the batch is diluted with water, filtered and recrystallized from acetonitrile. The product melts at 85° to 86°C

EXAMPLE 5 ##SPC18##

An oxime salt solution of 380 parts of 2.6-dichlorobenzaldehyde oxime, 46.3 parts of soidum in 4000 parts by volume of absolute ethanol is added drop by drop during 1 hour to a cooled mixture of 405 parts of 4-chloro-1,3-dinitrobenzene and 500 parts by volume of acetonitrile while stirring and at a rate such that the temperature remains between -5°C and +10°C. After 3 hours, the batch is diluted with ice water, filtered and recrystallized from dimethylformamide-acetonitrile. The product melts at 177° to 178°C.

EXAMPLE 6 ##SPC19##

An oxime salt solution of 43.5 parts of isobutyraldoxime and 10.5 parts of sodium in 300 parts by volume of absolute ethanol is added drop by drop during 30 minutes at -5°C to a mixture of 93 parts of 4-fluoro-1,3-dinitrobenzene and 200 parts by volume of acetonitrile, while stirring. The batch is then stirred for 3 hours at room temperature, diluted with ice water, filtered and recrystallized from acetonitrile. The product melts at 80° to 82°C.

EXAMPLE 7 ##SPC20##

A solution of 54 parts of the cyclohexanone oxime sodium salt in 800 parts by volume of dioxane is added drop by drop at room temperature during 30 minutes to a mixture of 106 parts of 4-chloro-3-nitrobenzenesulphonic acid-(1)-dimethylamide in 500 parts by volume of dioxan while stirring. During the addition, the temperature rises to 35°C. After 2 hours, the batch is heated for 1/2 hour at 50°C, than diluted with ice water, filtered, and recrystallized from ethanol. The product melts at 124° to 125°C.

EXAMPLE 8 ##SPC21##

An oxime salt solution prepared from 30 parts of 2-chlorobenzaldehyde oxime, 4.5 parts of sodium and 400 parts by volume of absolute ethanol is added drop by drop at room temperature, during 30 minutes, to a solution of 42 parts of 5-chloro-2,4-dinitraniline in 500 parts by volume of acetonitrile while stirring. After 6 hours, the whole is diluted with ice water, filtered and recrystallized from acetonitrile. The product melts at 166° to 167°C.

EXAMPLE 9 ##SPC22##

33 Parts of α-methylaminopropionitrile in 200 parts by volume of dioxan are added drop by drop within 1 hour at 50°C while stirring to 69 parts of couminaldehyde oxime-o-(5-chloro-2,4-dinitro-phenyl ether) in 700 parts by volume of dioxan, during which the temperature of the solution rises slightly.

After 1 hour, the batch is diluted with ice water, filtered and recrystallized from ethanol-dimethylformamide. The product melts at 161° to 162°C.

EXAMPLE 10 ##SPC23##

23 Parts of isopropylamine in 100 parts of dioxan are added drop by drop during 1 hour, at 50°C, to 77 parts of fluorenone oxime-o-(5-chloro-2,4-dinitrophenyl ether) in 1500 parts by volume of dioxan. The batch is then refluxed for 3 hours at 80°C, another 20 parts of isopropylamine are added and the mixture is heated for 3 hours at 80°C, diluted with ice water, filtered and digested with hot dimethylformamide. The product melts at 240° to 241°C with decomposition.

EXAMPLE 11 ##SPC24##

An oxime salt solution prepared from 86 parts of 3,4-dichlorobenzaldoxime, 10.3 parts of sodium and 600 parts by volume of absolute ethanol is added drop by drop at room temperature within 1/2 hour to 130 parts of isopropyl-(5-chloro-2,4-dinitrophenyl)-sulphide in 400 parts by volume of acetonitrile, while stirring. After 3 hours, the batch is diluted with ice water, filtered and recrystallized from acetonitrile. The product melts at 191° to 192°C.

EXAMPLE 12 ##SPC25##

A thiophenolate solution prepared from sodium methylate and 29 parts of 4-chlorothiophenol in 800 parts by volume of dioxan is added drop by drop, under a current of nitrogen, during 30 minutes, to 63 parts of 2-methoxybenzaldehydroxime-O-(5-chloro-2,4-dinitrophenyl ether) in 1000 parts by volume of dioxan, while stirring. The batch is then heated for 1 hour at 40°C, diluted with ice water, filtered and recrystallized from dioxan-dimethylformamide. The product melts at 197° - 198°C.

The following oxime ethers of 2,4-dinitrophenols have been prepared by analogous methods described in the foregoing Examples: ##SPC26##

                  Table 1                                                          ______________________________________                                         Compound                                                                              R.sub.1             Melting Point                                       No.    ∠C=           °C                                                  R.sub.2                                                                 ______________________________________                                         13                         165 - 166                                           14                         195 - 196                                           15                          197 - 197.5                                        16                         186 - 187                                           17                          189 - 190.5                                               O                                                                              ∥                                                              18     CH.sub.3 NH--C--O-- 181 - 182                                           19                         185 - 186                                           20                         199.5 - 200                                         21                         165 - 166                                           22                         164 - 165                                           23                         202 - 203                                           24                         184 - 185                                           25                         206.5 - 207                                         26                         142 - 144                                                  CH.sub.3                                                                27     ∠C=            71 - 71.5                                                 CH.sub.3                                                                28                         141 - 142                                           29                         143.5 - 144                                         30                          175 - 175.5                                        31                         195 - 196                                           32                         180 - 181                                                  CH.sub.3                                                                       |                                                              33     CH.sub.3 --(CH.sub.2).sub.6 --C=                                                                   yellow oil                                          34                         198.5 - 199                                         35                         200 - 201                                                                      (decomp.)                                                  CH.sub.3                                                                       |                                                              36     CH.sub.3 --C=        89 - 89.5                                          37                         196 - 197                                                  CH.sub.3                                                                       |                                                              38     CH.sub.3 --(CH.sub.2).sub.5 --C=                                                                   47 - 48                                                    CH.sub.3 CH.sub.3                                                              ∠                                                                        C--CH.sub.2                                                                    |                                                              39     CH.sub.2 ∠C=  85 - 97                                                    |                                                                     C=CH                                                                           |                                                                     CH.sub.3                                                                       CH.sub.3                                                                       |                                                                     CH.sub.2 --C                                                                   ||                                                    40     CH.sub.2 CH.sub.2 ∠C=                                                                         97 - 111                                                  ∠                                                                        CH--C                                                                          ∠                                                                        H.sub.3 C CH.sub.3                                                      41                         205 - 206                                                                      (decomp.)                                                  CH.sub.3                                                                       |                                                                     CH.sub.2 ----C                                                                 |                                                              42     CH.sub.2 C(CH.sub.3).sub.2 ∠C=                                                               107 - 109                                                  ∠                                                                        CH----CH.sub.2                                                          43                         188 - 190                                                  (CH.sub.3).sub.2 CH--CH.sub.2                                           44     ∠C=           75 - 77                                                    (CH.sub.3).sub.2 CH--CH.sub.2                                                  CH.sub.2 --CH.sub.2                                                            |                                                                     CH.sub.2                                                                45     |∠C= 81 - 83                                                    CH.sub.2                                                                       |                                                                     CH.sub.2 --CH.sub.2                                                            C.sub.2 H.sub.5                                                         46     ∠C=           91 - 92                                                    C.sub.2 H.sub.5                                                                CHCH.sub.3                                                                     ||                                                    47     CH.sub.3 --C--CH.sub.2 --C=                                                                        91 - 92                                                    |                                                                     CH.sub.3                                                                       CH.sub.3 CH.sub.3                                                              ||                                                    48     CH.sub.3 --CH--CH.sub.2 --C=                                                                       36 - 37                                                    CH.sub.3 CH.sub.3                                                              |∥                                                    49     CH.sub.3 --CH--(CH.sub.2).sub.2 --C=                                                               56 - 58                                             50                         177 - 178                                                                      (decomp.)                                           51                         161 - 163                                           52                         136 - 138                                                  CH.sub.3 CH.sub.3                                                              ||                                                    53     CH.sub.3 --C=CH--C= 130 - 131                                                  CH.sub.3                                                                       |                                                              54     --CH=CH--C=         136 - 142                                                  CH.sub.3                                                                55     |          183 - 184                                                  --CHBr--CHBr--C=    (decomp.)                                           56                         214 - 215                                           57                         185 - 186                                           58                         210 - 211                                           59                         187 - 189                                           60                         155 - 156                                           61     CH.sub.3 --CH=       95 - 96.5                                           61 a                      194 - 195                                                                      (decomp.)                                           ______________________________________                                    

The following oxime ethers of 2,4-dinitro-5-chlorophenol were prepared by methods analogous to those described in the foregoing Examples: ##SPC27##

                  Table 2                                                          ______________________________________                                         Compound                                                                               R.sub.1               Melting Point                                    No.                           °C                                                ∠C=                                                                      R.sub.2                                                                ______________________________________                                                 CH.sub.3                                                               62      ∠CH--           130 - 131                                                CH.sub.3                                                                       CH.sub.3                                                               63      ∠C=             92 - 94                                                  CH.sub.3                                                               64                            85 - 87                                          65                            168 - 169                                                CH.sub.3                                                                       |                                                             66      C.sub.2 H.sub.5 --C=  72 - 74                                          67                            186 - 187                                                                      (decomp.)                                                CH.sub.3                                                                       |                                                                     CH.sub.2 ------C                                                               ||                                                   68      CH.sub.2 C(CH.sub.3).sub.2 ∠C=                                                                 126 - 127                                                ∠|                                                              CH------CH.sub.2                                                       69                            175 - 176                                        70                            169 - 170                                        71                            182 - 183                                        72                            202 - 203                                                CH.sub.3                                                                       |                                                             73      CH.sub.3 --CH--C=     68 - 69                                                  |                                                                     CH.sub.3                                                                       CH.sub.3 CH.sub.3                                                              ∠                                                                        C--CH.sub.2                                                                    |                                                             74      CH.sub.2 ∠C=    110 - 112                                                |                                                                     C=CH                                                                           |                                                                     CH.sub.3                                                                       CH.sub.3                                                                       |                                                                     CH.sub.2 --C                                                                   ||                                                   75      CH.sub.2 CH.sub.3 ∠C=                                                                          104 - 105                                                ∠                                                                        CH--C                                                                          ∠                                                                        CH.sub.3 CH.sub.3                                                              CH.sub.3                                                                       |                                                             76      CH.sub.3 --(CH.sub.2).sub.6 --C=                                                                     brown oil                                        77                            165 - 166                                        78                            181 - 183                                                CH.sub.3 CH.sub.3                                                              ||                                                   79      CH.sub.3 --C=CH--C=   brown oil                                                C.sub.2 H.sub.5                                                                |                                                             80      CH.sub.3 -- (CH.sub.2).sub.3 --C=                                                                    brown oil                                                CH.sub.3                                                                       |                                                             81      --CH=CH--C=           155 - 165                                                CH.sub.3 C.sub.2 H.sub.5                                                       ||                                                   82      C.sub.2 H.sub.5 --CH--CH.sub.2 --C=                                                                  brown oil                                        83                            128 - 131                                        84                            132 - 133                                        85                            148 - 149                                                CH.sub.3 CH.sub.3                                                              ||                                                   86      CH.sub.3 --CH--CH.sub.2 --C=                                                                         brown oil                                                CH.sub.3                                                                       |                                                             87      --CHBr--CHBr--C=      186 - 187                                        88                            214 - 215                                        88 a                          194 - 196                                                                      (decomp.)                                        88 b                          187 - 189                                                                      (decomp.)                                        88 c                          176 - 178                                                                      (decomp.)                                        ______________________________________                                    

The following oxime ethers of 2-nitro-4-carbomethoxyphenol were prepared by methods analogous to those described in the foregoing Examples: ##SPC28##

                  Table 3                                                          ______________________________________                                         Compound  R.sub.1           Melting point                                      No.       ∠C=         °C                                                    R.sub.2                                                              ______________________________________                                         89                          68 - 69                                            90                          135 - 137                                          91                          134 - 136                                          92                          169 - 171                                          93                          185 - 186                                                    CH.sub.3                                                                       |                                                           94        C.sub.2 H.sub.5 --C=                                                                             68 - 69                                                      C.sub.2 H.sub.5                                                                |                                                           95        C.sub.2 H.sub.5 --C=                                                                             brown oil                                                    CH.sub.3                                                             96        ∠CH--       143 - 144                                                    CH.sub.3                                                              96 a                       175 - 176                                                                      (decomp.)                                           96 b                       181 - 182                                                                      (decomp.)                                          ______________________________________                                    

The following oxime ethers of 2,4-dinitro-6-carbomethoxyphenol were prepared in a similar manner: ##SPC29##

                  Table 4                                                          ______________________________________                                         Compound R.sub.1           Melting point                                       No.      ∠C=         °C                                                    R.sub.2                                                               ______________________________________                                          97                        124 - 126                                            98                        50 - 51                                              99                        105 - 107                                           100                        123 - 124                                           101                        133 - 135                                                    CH.sub.3                                                                       |                                                            102      CH.sub.3 --C=     65 - 67                                                      CH.sub.3 CH.sub.3                                                              ||                                                  103      CH.sub.3 --C----C=                                                                               brown oil                                                    |                                                                     CH.sub.3                                                                       CH.sub.3 CH.sub.3                                                              ||                                                  104      CH.sub.3 --CH--CH.sub.2 --C=                                                                     brown oil                                                    CH.sub.3                                                                       |                                                            105      --CH=CH--C=       141 - 143                                           106                        119 - 120                                           107                        121 - 122                                           108                        131 - 132                                           109                        156 - 157                                                    C.sub.2 H.sub.5                                                                |                                                            110      CH.sub.3 --(CH.sub.2).sub.3 --C=                                                                 brown oil                                                    CH.sub.3 CH.sub.3                                                              ||                                                  111      CH.sub.3 --CH--(CH.sub.2).sub.2 --C=                                                             brown oil                                                    C.sub.2 H.sub.5                                                                |                                                            112      C.sub.2 H.sub.5 --C=                                                                             brown oil                                                    CH.sub.3                                                                       |                                                            113      --CH=CH--C=       141 - 143                                                    CH.sub.3 C.sub.2 H.sub.5                                                       ||                                                  114      C.sub.2 H.sub.5 --CH--CH.sub.2 --C=                                                              brown oil                                            114 a                     165 - 167                                           ______________________________________                                    

The following oxime ethers of 2,4-dinitro-6-carboxyclorexoxy were prepared in a similar matter: ##SPC30##

                  Table 5                                                          ______________________________________                                         Compound    R.sub.1        Melting point                                       No.         ∠C=      °C                                                       R.sub.2                                                            ______________________________________                                         115                        130 - 132                                                       CH.sub.3                                                           116         ∠CH--    122 - 123                                                       CH.sub.3                                                           117                        111 - 113                                                       OHCH.sub.3                                                                     ||                                               118         CH.sub.3 --C--CH.sub.2 --C=                                                                   brown oil                                                       |                                                                     CH.sub.3                                                                       C.sub.2 H.sub.5                                                    119         ∠C=      brown oil                                                       C.sub.2 H.sub.5                                                                CH.sub.3                                                                       |                                                         120         C.sub.2 H.sub.5 --C=                                                                          75 - 76                                             ______________________________________                                    

Furthermore, the following oxime ethers of 2-nitro-4-formylphenol were prepared analogously: ##SPC31##

                  Table 6                                                          ______________________________________                                         Compound R.sub.1          Melting point                                        No.      ∠C=        °C                                                     R.sub.2                                                               ______________________________________                                         121                       197 - 198                                            122                       143 - 144                                             122 a                    190 - 191                                                                      (decomp.)                                            ______________________________________                                    

Furthermore, the following oxime ethers of 2-nitro-4-trifluoromethylphenol were prepared analogously: ##SPC32##

                  Table 7                                                          ______________________________________                                         Compound                                                                               R.sub.1               Melting point                                    No.                            °C                                               ∠C=                                                                      R.sub.2                                                                ______________________________________                                         123                           143 - 144                                                CH.sub.3                                                                       |                                                                     CH.sub.2 --C                                                                   |                                                             124     CH.sub.2 CH.sub.2 ∠C=                                                                          83 - 85                                                  ∠                                                                        CH--C                                                                          ∠                                                                        CH.sub.3 CH.sub.3                                                      124 a                         149 - 151                                                                      (decomp.)                                        124 b                         182 - 183                                                                      (decomp.)                                        ______________________________________                                    

The 2,6-dinitro-4-trifluoromethylphenyl ether of the acetonoxime (compound No. 125) melts at 80° - 81°C.

Furthermore, the following oxime ethers of 2,4,6-trinitrophenol were manufactured analogously: ##SPC33##

    Compound                                                                               R.sub.1               Melting point                                    No.                           °C                                                ∠C=                                                                      R.sub.2                                                                ______________________________________                                         126                           164 - 165                                        127     CH.sub.3              114 - 115                                                ∠C=                                                                      CH.sub.3                                                               128                           147 - 148                                                CH.sub.3                                                               129     ∠HC--           157 - 158                                                CH.sub.3                                                               ______________________________________                                    

The following oxime ethers of 2-nitro-4-N,N-dimethylsulphamylphenol were manufactured analogously: ##SPC34##

                  Table 8                                                          ______________________________________                                         Compound                                                                               R.sub.1               Melting point                                    No.                            °C                                               ∠C=                                                                      R.sub.2                                                                ______________________________________                                         130                           183 - 184                                        131                           174 - 176                                                CH.sub.3                                                                       CH.sub.2 ------C∠                                                        |                                                             132     CH.sub.2 CH.sub.3 --C--CH.sub.3 C=                                                                   142 - 144                                                ∠|                                                              CH------CH.sub.2                                                       133     CH.sub.3 --CH--C=     111 - 113                                                ||                                                           CH.sub.3 CH.sub.3                                                      133 a                         184 - 185                                                                      (decomp.)                                        ______________________________________                                    

The cyclohexanone oxime-2-nitro-4-N-methylsulphamylphenyl ether (compound 134) melts at 129° - 130°C.

Furthermore, the following oxime ethers of 2,4-dinitro-5-aminophenol were manufactured analogously: ##EQU2##

The following oxime ethers of 2,4-dinitro-5-isopropylaminophenol were manufactured analogously: ##SPC35## ##EQU3##

The following oxime ethers were also manufactured in an analogous way to that described above ##EQU4##

EXAMPLE 13

a. A mixture of 50 g of the active ingredient No. 14, 20 g of Hisil (a silica preparation), 25 g of kaolin, 3.5 g of flotation agent (for example a condensation product of 1 mol of para-octylphenol with 6 to 10 mols of ethylene oxide) and 1.5 g of a wetting agent (for example the sodium salt of 1-benzyl-2-heptadecylbenzimidazole-disulphonic acid) is finely ground to form a wettable powder containing 50% of the active product.

The active ingredient No. 21 is formulated in a similar manner, except that 25 g of chalk are used instead of 25 g of kaolin. In an identical manner, the active substance No. 14 of Example 4 is formulated.

b. 500 Grams each of the active ingredients Nos. 5 and 67 are mixed with 110 g of ammonium ligninsulphonate, 45 g of dicresyl methanedisulphonic acid, 10 g of a mixture of 40% of an alkylarylpolyether alcohol and 60% of magnesium carbonate, and 335 g of kaolin. In each case, the resulting mixture may be diluted with water to form a stable emulsion.

EXAMPLE 14

a. When used for a postemergence treatment, the following active compounds produced a good effect against a variety of dicotyledonous plants.

The above mentioned treatment was carried out with 5.0 kg each of the active compounds listed below 12 days after sowing, when the plants had developed 1 to 2 genuine leaves.

The following results were recorded:

    Species Comp.                                                                  of plant                                                                               No. 1                                                                              No. 2                                                                             No. 13                                                                             No. 14                                                                             No. 15                                                                              No. 17                                                                              No. 18                                                                              No. 19                                                                              No. 21                                                                              No. 26                                                                              No.                                                                                 No.                  __________________________________________________________________________                                                               29                   Beta vulgaris                                                                          9   9  9   9   9    10   10   9    10   10   10   10                   Calendula                                                                              9   10 10  10  10   10   10   10   8    10   10   9                    Linum   10  8  8   10  10   10   10   10   8    10   10   10                   Brassica                                                                               9   10 10  10  9    10   10   9    10   10   10   10                   Daucus  9   10 10  9   2    8    10   10   8    9    8    2                    Lactuca 10  10 10  10  2    5    10   10   10   10   10   2                    Medicago                                                                               2   4  4   10  6    10   10   9    10   10   10   10                   Soya    1   2  9   10  1    4    8    7    8    4    1    1                    Triticum                                                                               0   0  0   1   0    0    0    0    0    1    1    1                    Hordeum 2   1  2   0   2    3    3    2    1    3    2    1                    Sorghum 1   1  0   1   1    2    4    1    2    2    1    1                    Phaseolus                                                                              4   9  5   4   2    6    5    9    7    4    5    1                    __________________________________________________________________________

    Species Comp.                                                                  of plant                                                                               No. 32                                                                              No. 33                                                                              No. 36                                                                              NO. 37                                                                              NO. 41                                                                              No. 43                                                                              No. 46                                                                              No. 47                                                                              No. 56                                                                              No.                                                                                 No.                  __________________________________________________________________________                                                               65                   Beta vulgaris                                                                          9    8    10   10   10   10   10   10   10   10   10                   Calendula                                                                              8    7    10   9    10   10   10   10   8    10   10                   Linum   10   7    10   10   10   8    9    9    7    10   10                   Brassica                                                                               10   8    10   10   10   10   10   10   10   10   10                   Daucus  10   6    10   9    9    8    8    10   8    8    6                    Lactuca 8    5    10   9    10   10   10   10   9    8    8                    Medicago                                                                               2    2    2    3    6    10   10   10   6    8    9                    Soya    0    0    0    0    0    8    1    1    6    1    1                    Triticum                                                                               0    0    0    0    0    0    1    0    0    0    1                    Hordeum 2    1    1    1    0    0    1    0    0    0    0                    Sorghum 1    1    2    2    1    0    0    1    0    0    1                    Phaseolus                                                                              4    7    8    4    5    8    4    2    4    1    4                    __________________________________________________________________________

    Species No.                                                                               No. No. No. No. No. No. No. No. No. No. No. No. No.                 of plant                                                                               71 72  88  91  92  93  97  98  100 101 109 121 130 131                 __________________________________________________________________________     Beta vulgaris                                                                          10 10  10  8   8   10  8   10  10  10  10  8   10  8                   Calendula                                                                              10 10  10  8   10  10  10  10  10  10  8   7   8   10                  Linum   10 10  10  8   10  8   10  10  10  10  8   8   10  10                  Brassica                                                                               10 8   10  10  10  8   8   10  10  8   8   10  8   6                   Daucus  6  10  10  9   5   10  8   10  8   8   8   10  10  10                  Lactuca 8  10  10  9   10  8   5   10  8   10  10  9   10  10                  Medicago                                                                               10 8   10  6   10  10  10  10  8   10  10  10  8   8                   Soya    1  1   1   5   8   10  8   1   1   8   8   2   10  10                  Triticum                                                                               0  0   1   0   1   0   1   1   1   0   0   0   0   0                   Hordeum 0  0   0   1   0   0   0   1   0   1   1   1   1   1                   Sorghum 2  2   1   0   1   0   1   0   1   0   0   0   1   1                   Phaseolus                                                                              8  6   7   5   4   7   8   8   5   10  10  6   4   5                   __________________________________________________________________________      Explanation:                                                                   O = no effect                                                                  <5 = damage that spreads                                                       >5 = damage that results in the plant dying off                                10 = plant completely destroyed.                                         

Each of the active compounds Nos. 5, 10, 20, 56, 67, 88 and 99,formulated as described in Example 13b was sprayed on the soil in an amount of 0.5 kg per hectare, in a greenhouse test immediately after sowing -- i.e. by the preemergence method. The test plants and the results achieved are listed in the following Table:

    Species of                                                                             Comp.    No.     No.   No.  No.  No.  No.                              plant   No. 5    10      20    56   67   88   99                               ______________________________________                                         Triticum                                                                               2        2       2     2    2    1    1                                Hordeum 2        2       1     1    2    2    1                                Avena   10       8       8     8    8    10   8                                Poa     10       10      10    10   10   10   8                                Dactylis                                                                               10       10      10    10   10   10   10                               Linum   3        3       5     5    3    5    10                               Brassica                                                                               3        3       2     2    1    0    0                                Lactuca 10       8       8     10   10   10   10                               Medicago                                                                               4        5       8     8    8    10   8                                Soya    1        1       1     1    1    0    0                                Phaseolus                                                                              1        1       0     1    0    1    0                                ______________________________________                                          O = no effect                                                                  10 = plant completely destroyed                                          

When applied in an amount of 0.5 kg of active compound only a few plants were strongly affected, above all Avena, Poa, Dactylis and Lactuca, whereas the others were not damaged at all or only to a very small extent, such as Triticum, Hordeum, Brassica, Soya and Phaseolus.

b. The active substances Nos. 5 and 67, formulated as described in Example 13b, in an amount of 4.0, 2.0, 1.0 and 0.5 kg of active substance per hectare, were sprayed over the soil in a greenhouse test immediately after seeding, that is to say, by the pre-emergence method. The seedlings treated and the results achieved are shown in the following Table:

    Active substance No. 5                                                                             Active substance No. 67                                     4        2      1    0.5 kgAS                                                                                4  2     1  0.5 kgAS                            ______________________________________                                         Triticum                                                                              10    10     9   2       10  7     7  2                                 Hordeum                                                                               10     5      5  2       10  4     5  2                                 Avena  10    10     10  10      10  10   10  8                                 Poa    10    10     10  10      10  10   10  10                                Dactylis                                                                              10    10     10  10      10  10   10  10                                Linum  10    10     10  3       10  9     8  3                                 Brassica                                                                              10    10      5  3       10  4    2   1                                 Lactuca                                                                               10    10     10  10      10  10   10  10                                Medicago                                                                              10    10     10  4       10  10   10  8                                 Soya   10     7      4  1        9  4     2  1                                 Phaseolus                                                                              5     1      1  1        4  1     0  0                                 ______________________________________                                          0 = no effect                                                                  10 = plant completely destroyed                                          

When applied in an amount of 4.0 kg per hectare both these products of the invention displayed a broad effect, whereas with 0.5 kg of active substance only some plants were strongly effected, above all Avena, Poa, Dactylis and Lactuca, whereas others were not damaged at all or only very little, for example Triticum, Hordeum, Brassica, Soya and Phaseolus.

Accordingly, the two new active substances may be used as total herbicides by the pre-emergence method or, when used in a suitable concentration, for the selective control of weeds, for example in grain crops (Triticum and Hordeum), varieties of cabbage (Brassica) and leguminoses (soybeans and phaseolus beans).

EXAMPLE 15

Mixtures containing 50 g of the active substances Nos. 16, 20, 22, 4 and 66 each, 3.5 g of a non-ionic, and 1.5 g of an anionic wetting and dispersing agent are finely ground with 50 g of a vehicle. The wettable spray powders thus obtained may be diluted with water in any desired proportion.

EXAMPLE 16

10 to 40 Grams of each of the compounds 68, 73, 75, 98 76 and 94 are made up with an adequate amount of an emulsifier (sulphonate-nonionic mixture) in xylene to a volume of 100 ml. These emulsion concentrates may be diluted with water to the desired concentration and used as fungicides.

EXAMPLE 17

The products of this invention, for example compound No. 16, are also distinguished by their action against genuine powdery mildew. Zucchetti plants (Cucumis pepo) were trained in a greenhouse and once sprayed prophylactically with a broth containing as active ingredient 0.2 % of the preparation formulated as described in Example 15. 2 Days after having been sprayed, the plants were infested with spores of Erysiphe cichoracearum and 12 to 14 days later checked for fungus attack. Compared with the untreated control (effect: nil) the sprayed plants displayed a 90% effect without having developed phytotoxic damage.

Effects similar to those against Erysiphe cichoracearum described above were observed with the following compounds, which were readily tolerated by the Zucchetti plants:

    Compound No.     Effect in %                                                   ______________________________________                                         20               80                                                             4               100                                                           49               95                                                            66               80                                                            ______________________________________                                    

EXAMPLE 18

The action of the compounds of this invention against leaf spot fungi was confirmed on celery (Apium graveolens) with the fungus Septoria apii. Celery plants were trained in a greenhouse and, 2 days before infection with the fungus Septoria, sprayed with broths each containing 0.2 % of one of the active compounds mentioned below. After infection, the plants were placed for 2 to 3 weeks in an incubation room having a high atmospheric humidity and then checked for infestation against an untreated control series, which latter revealed a nil-return. The effects produced by the compounds of this invention are listed in the following Table:

    Compound No.     Effect in %                                                   ______________________________________                                         20               93                                                            22               80                                                             4               93                                                            66               100                                                           68               94                                                            73               100                                                           75               95                                                            98               94                                                            76               100                                                           94               87                                                            80               100                                                           ______________________________________                                    

EXAMPLE 19 Herbicidal effect in the greenhouse

    Preemergent         Postemergent                                               compound No. 99     compound No. 93                                            KgAS       2.0    1.0    0.5  0.25  5.0    2.5                                 ______________________________________                                         Triticum   10     10      9   7      0     0                                   Hordeum    10      9      7   4      0     0                                   Avena      10     10     10   10     1     1                                   Sorghum     8      4      2   1      2     1                                   Panicum    10     10      8   1     10     8                                   Poa        10     10     10   8      6     2                                   Dactylis   10     10     10   10     4     2                                   Digitaria  10     10      4   1      7     4                                   Beta       10     10     10   10    10     10                                  Calendula  10     10     10   10    10     10                                  Linum      10     10     10   5     10     10                                  Brassica   10     10      7   8     10     10                                  Daucus     10     10     10   10    10     10                                  Lactuca    10     10     10   10    10     10                                  Soya       10      8      2   0      4     3                                   Phaseolus  10     10      1   0      8     5                                   ______________________________________                                    

When compound No. 99 was applied in an amount of 2 kg or over, it displayed total herbicidal properties.

When a small amount, for example 0.25 kg, of the active substance of this invention is applied, numerous test plants can be completely or almost completely destroyed without affecting, for example, soybean or phaseolus bean plants. With even smaller amounts wild oats (Avena fatua) in barley (Hordeum) may be controlled.

Compound No. 93, applied in an amount of 2.5 kg, was successfully applied against numerous dicotyledons and Panicum, whereas the various types of grain crops were not damaged by the active substance of the invention.

EXAMPLE 20 Test on Grain Crops in the Field

In a field of winter wheat which had just been tilled and in which the weeds had reached the 4-leaf stage, the compounds Nos. 18 and 26 were sprayed in an amount of 8.0 kg per hectare. 3 Weeks after the treatment, the effects achieved on weeds were found to be very good (that is to say value 1 and 2 respectively). Grain crops, on the other hand, had not been damaged (value 1-2).

Test on salad in the open

The compound No. 27 was sprayed in an amount of 8.0 kg per hectare on salad four weeks after seeding (3-4 leaf stage) and when the weeds had reached the stage of the large rosette.

The effect achieved on the weeds was good (value 3), whereas the salad was not affected by the herbicide of this invention.

Tests with marrow cabbage in the open

Immediately after seeding marrow cabbage and before the weeds had emerged, the soil surface was sprayed with the compounds Nos. 5 and 67 of this invention each being used in amounts of 2.0, 3.0 and 4.0 kg per hectare. The effect achieved and the tolerance observed are shown in the Table, where the following values are used: For effect on weeds 1 = very good, 9 = effect nil. For tolerance by culture plants: 1 = very good, 9 = total destruction.

    Amount used                                                                               Compound No. 5  Compound No. 67                                     kg AS/ha   2.0     3.0     4.0   3.0    4.0                                    ______________________________________                                         effect on weeds                                                                           3       3       2     2      2                                      tolerance by                                                                   culture plants                                                                            2       2       2     3      5                                      ______________________________________                                    

EXAMPLE 21

All compounds to be tested were formulated in the usual manner.

To check their acaricidal effect, Phaseolus plants in the 2-leaf stage were infested 12 hours before the treatment by covering them with pieces of leaves infested by a mite species (Tetranychus telarius or Tetranychus urticae; carmine red mite). 12 Hours later, the test plant was found to be covered with mites in all stages of development. The active ingredient, in the form of an emulsion, was sprayed with the aid of a fine sprayer over the plants in a manner such that a uniform layer of droplets was formed on the leaf surface. The mortality was checked 2 and 7 days later and expressed in percent. The effect upon ova cannot be stated after the test had been run for 2 days as described because the average time taken by the larvae to leave the ova has not yet been established.

At a concentration of 0.08 % of active ingredient the following mortality values were found:

                         Ova       Larvae Adults                                   Comp.  After 2 days  --        100%   100%                                     No. 1  After 7 days  100%      100%   100%                                     ______________________________________                                         2      After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     3      After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     4      After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     5      After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     13     After 2 days  --        100%   100%                                            After 7 days   80%      100%   100%                                     14     After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     15     After 2 days  --        100%   100%                                            After 7 days   90%      100%   100%                                     29     After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     31     After 2 days  --        100%   100%                                            After 7 days   80%      100%   100%                                     45     After 2 days  --        100%   100%                                            After 7 days   80%      100%   100%                                     46     After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     58     After 2 days  --        100%   100%                                            After 7 days   80%      100%   100%                                     72     After 2 days  --        100%   100%                                            After 7 days   80%      100%   100%                                     78     After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     91     After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     101    After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     115    After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     123    After 2 days  --        100%   100%                                            After 7 days  100%      100%   100%                                     ______________________________________                                    

Compound No. 4, applied in a concentration of 0.05%, displayed a good killing effect against red spiders, for example against Panonychus ulmi, Eotetranychus tiliae a good killing effect, in fact against both their ova and the postembryonal stages.

The following compounds show at concentrations of 0.05 % the following mortality rate (ovicidal effect) against panonychus ulmi. (control after 7 days)

    Compound No.     Mortality rate in %                                           ______________________________________                                          3                95                                                            9               100                                                           10               100                                                           21               100                                                           56               100                                                           62                80                                                           78               100                                                           82               100                                                           88               100                                                           95               100                                                           119              100                                                           129              100                                                           ______________________________________                                    

In the following tables also Tetranychus urticae which is resistent to phosphorus acid esters is listed.

Compound No. 153

a. action against Tetr. urticae

    Mortality                                                                      after 2 days      after 7 days                                                 Conc. (ppm)                                                                            Larvae   Adults   Ova    Larvae Adults                                 ______________________________________                                         800     100      100      100    100    100                                    400     100      100      100    100    100                                    200     100      100       80     80    100                                    100     100      100       0      80     80                                    ______________________________________                                    

b. action against Tetr. telarius

    Mortality                                                                      after 2 days      after 7 days                                                 Conc. ppm                                                                              Larvae   Adults   Ova    Larvae Adults                                 ______________________________________                                         800     100      100      100    100    100                                    400     100      100      100    100    100                                    200     100      100       80     80    100                                    100     100      100       0      60     80                                    ______________________________________                                    

Compound No. 154

a. action against Tetr. urticae

    Mortality                                                                      after 2 days      after 7 days                                                 Conc. ppm                                                                              Larvae   Adults   Ova    Larvae Adults                                 ______________________________________                                         800     100      100      60     100    100                                    400     100      100      0       80    100                                    200     100      100      0       60     80                                    100     100      100      0       0      80                                    ______________________________________                                    

b. Action against Tetr. telarius

    Mortality                                                                      after 2 days      after 7 days                                                 Conc. ppm                                                                              Larvae   Adults   Ova    Larvae Adults                                 ______________________________________                                         800     100      80       0      100    100                                    400     100      80       0      100    100                                    200     100      80       0       80     80                                    ______________________________________                                    

Compound No. 155

a. Action against Tetr. urticae

    Mortality                                                                      after 2 days      after 7 days                                                 Conc. ppm                                                                              Larvae   Adults   Ova    Larvae Adults                                 ______________________________________                                         800     100      100      60     100     80                                    400     100      100      0       80    100                                    200     100      100      0       0     100                                    ______________________________________                                    

b. Action against Tetr. telarius

    Mortality                                                                      after 2 days      after 7 days                                                 Conc. ppm                                                                              Larvae   Adults   Ova    Larvae Adults                                 ______________________________________                                         800     100      80       0      100    100                                    400     100      80       0       80    80                                     200      80      80       0       0     80                                     ______________________________________                                    

Compound No. 156

a. Action against Tetr. urticae

    Mortality                                                                      after 2 days      after 7 days                                                 Conc.ppm                                                                               Larvae   Adults   Ova    Larvae Adults                                 ______________________________________                                         800     100      100      100    100    100                                    400     100      100      100    100    100                                    200     100      100       80    100    100                                    100     100      100       60     80    100                                    ______________________________________                                    

b. Action against Tetr. telarius

    Mortality                                                                      after 2 days      after 7 days                                                 Conc.ppm                                                                               Larvae   Adults   Ova    Larvae Adults                                 ______________________________________                                         800     100      100      100    100    100                                    400     100      100      100    100    100                                    ______________________________________                                    

Compound No. 157

a. Action against Tetr. urticae

    Mortality                                                                      after 2 days      after 7 days                                                 Conc.ppm                                                                               Larvae   Adults   Ova    Larvae Adults                                 ______________________________________                                         800     100      100      60     100    100                                    400     100      80       80     80     100                                    200      80      80       60     80      80                                    100      80      60        0     60      60                                    ______________________________________                                    

b. Action against Tetr. telarius

    Mortality                                                                      after 2 days       after 7 days                                                ______________________________________                                         Conc.ppm Larvae   Adults   Ova   Larvae Adults                                 ______________________________________                                         800      100      80       80    80     100                                    400      100      80       80    80     80                                     200       80      80       60    60     80                                     100       60       0        0     0     60                                     ______________________________________                                    

Compound No. 159

a. Action against Tetr. urticae

    Mortality                                                                      after 2 days       after 7 days                                                ______________________________________                                         Conc.ppm Larvae   Adults   Ova   Larvae Adults                                 ______________________________________                                         800      80       80       60    100    100                                    400      80       80       60    80     100                                    200      80       80       60    60      0                                     100      80       80        0     0      0                                     ______________________________________                                    

b. Action against Tetr. telarius

    Mortality                                                                      after 2 days       after 7 days                                                ______________________________________                                         Conc.ppm Larvae   Adults   Ova   Larvae Adults                                 ______________________________________                                         800      80       80       80    100    100                                    400      80       80       80    80     100                                    200      80       60       60    60      0                                     100      60        0        0     0      0                                     ______________________________________                                    

Compound No. 160

a. Action against Tetr. urticae

    Mortality                                                                      after 2 days       after 7 days                                                ______________________________________                                         Conc.ppm Larvae   Adults   Ova   Larvae Adults                                 ______________________________________                                         800      100      100      80    100    100                                    400      100      100      80    100    100                                    200      100      100      80    100    100                                    100      100      100      60     80    100                                    ______________________________________                                    

b. Action against Tetr. telarius

    Mortality                                                                      after 2 days       after 7 days                                                ______________________________________                                         Conc.ppm Larvae   Adults   Ova   Larvae Adults                                 ______________________________________                                         800      100      100      80    100    100                                    400      100      100      80    100    100                                    200      100      100      60     80    100                                    100      100      100      60     80    100                                    ______________________________________                                    

EXAMPLE 22

Compound No. 4, applied in a concentration of 0.05 %, displayed a good killing effect against red spiders, for example against Panonychus ulmi, Eotetranychus tiliae in fact against both their ova and the postembryonal stages.

Equally good results were observed with compounds Nos. 21 and 3.

EXAMPLE 23

Freshly laid ova of the flour moth Ephestia Kuehniella (20 each) were placed in folded paper filters, the emulsified compound No. 36 was poured over them and they were then spread open and allowed to dry at room temperature. When the filter had completely dried, each moth tested was covered with a wire net and kept until the untreated control moth had left its ovum. The checking of the effects was carried out under a binocular microscope and revealed the following total destruction (active substance in parts per million):

    Concentration of active                                                        substance in ppm                                                                              1000    500    250  125   62.5                                  % killed        100    100    100  100    100                              

I claim:
 1. A compound of the formula ##SPC36##in which X is chlorine, bromine or iodine. 